Carbonaceous product



June 30, 1931. R. T. GOODWIN CARBONACEOUS PRODUCT KS. www. NRT@ RALPH T. @Loowm Patented June 30, 1931 UNITED STATES PATENT OFFICE RALPH T. GOODWIN, F ELIZABETH, NEW JERSEY, ASSIGNOR IO STANDARD OIL DEVELOPMENT COMPANY, A CORPORATION 0F DELAWARE CARBONACEOUS PRODUCT Application led February 18, 1926'. Serial No. 89,059.

This invention relates to the production of solid or semi-solid carbonaceous materials by treatment of hydrocarbon oils. In my United States Patents Nos. 1,660,294 and 1,660,295,

's granted February 21, 1928, of which the present application is a continuation in part, I have described and claimed methods for rapidly precipitating non-liquid carbonaceous substances from oils characterized by the tendenc to deposit such substances slowly on stan ing.

The present invention is directed more particularly to the preparation and purification ofthe carbonaceous product from oils ,of the type described. I have found that this product has unique properties and is commercially valuable for a number of uses. For brevity it is referred to herein as carbon, since that element ordinarily forms 85% or more of its mass. There are certain other characteristie components of the product, however, as

will be more fully discussed further on. The

*carbon is further referred to as precipitated, within lwhich term are included settling out, sedimentation, and the like.

The invention will be understood from the following description, taken in connection with the accompanying drawing, in which the figure is a diagrammatic side eleva-tion of suitable equipment for carrying out the process. Referring to the drawing, reference numeral ldenotes a mixer of any approved type, into which a carbon-precipitating agent 1s introduced from tank 2 through pipe 3. As described in my earlier applications, this reagent may bean acidicbody, preferably in small amount, for example 30 B. sulfuric acid in amount about 0.5% by volume of the oil. Instead of sulfuric acid, other acidic reagents may be used, for example, dilute 'hydrochloric acid, dilute acetic acid and dilute solutions of salts such as sodium acid sulfate or aluminum sulfate which hydrolyze to form acids. A calibrated container 4 may be installed in the pipe 3 to facilitate measuring the acid reagent, which is supplied to the tank 2 through pipe 5. Air or other pressuretransmitting medium is introduced through pipe 6. Valves are arranged throughout the 50 equipment for regulating the flow of gases and liquids, as shown in the drawing, and other suitable valves may be supplied to meet special requirements.

The oil to be treated is passed into the mixer 1 through pipe 7. Especially desirable sources of my improved carbon product are heavy residues from oil crackingA equipment such as pressure stills, cracking coils, and the like. The invention is also applicable, however, to other oils that tend to deposit carbon or carbonaceous sediment in an analogous manner for example semi-cracked material such as crude still tar. Various blends of oils may be used. It is desirable to treat the oil hot, say at a temperature of 140 C. For heat economy the'oil should be treated before it has lost the heat acquire-d in the cracking operation or other heat treatment.

The oil and acid, after commingling in the mixer 1, are discharged through pipe.8, having a gas vent pipe 9. The pipe 8 is connected with agitatorsilO and 11 by by-pass y. pipes 12 -and 13. In the agitators the oil and acid are brought into intimate contact and the mixture is drawn off through pipe 14 by pump 15 which discharges it through pipe 16 into a thickener 17. The pipe 8 is continued past the by-pass lines 12 and 13 to the pipe 16,

forin 'some cases it may be desirable to omit the agitation and discharge the mixture directly into the thickener. Mechanical stirrers, or agitation by gas or air introduced through pipe 18, may be provided in agitators 10 and 1l. `The agitators may be used alternately or together.

The thickened, carbon-containing oil is drawn 0H from the bottom of the thickener through pipe 19 by pump 20 and discharged through pipe 21 to the filter 22, which may be of the rotary continuous type operated by suction, lof the pressure type, or other suitable form. The oil separated from the carbon is withdrawn from the thickener through one or more of the outlet pipes 23 to pipe 24. Suction is exerted through this pipe by pump 25 which draws the oil to receivers 26. A cooler 27 is interposed in pipe 24 for use when desired.

When using the rotary continuous type of filter, the carbon is retained by it, and the clarified oil residue passes through the cooler 28 and pipe 29 to auxiliary receivers 30, one or the other or both of which may be used as required. The auxiliary receivers are connected through pipe 31 with a main receiver 32 which is in turn connected by a pipe 33 with the pipe 24;. A vacuum pump 34 maintains a reduced pressure in auxiliary receivers 30 through main pipe 35 and branch pipes 3G and 37. The filter 22, being con neeted to the receivers, is also subjected to the effect of the vacuum pump.` Atmospheric pressure forces the liquid through the filter blanket in the well-known manner. A check valve 38, a seal 39, and a safety relief vent 40 are arranged in connection with the pipe 35. A steam engine 42, or other suitable source of power, may be supplied.

The carbon product may be removed from the filter through the conveyor ll for extrae* tion and subsequent treatment in other apparatus. When using the closed, pressure type filter, I prefer to extract the carbon on the filter. Any suitable solvent may be used, for example carbon disulfid, carbon tetrachlorid, acetone, benzol, naphtha, and the like. A solvent such as carbon disulfid removes any residual oil and most of, if not all, the heavy hydrocarbon compounds of asphaltic nature which maybe associated with the carbon. The carbon is next blown free from the solvent in the filter and is then in substantially pure condition, ready for any desired utilization, for example in the manufacture of electrodes, as a rubber filler, and for other uses. Drying or other suitable expedients for removing residual solvent may be adopted instead of blowing.

When the carbon is to be used for certain purposes, for example as a binder for fuel briquettes, it is desirable to omit the extraction. The residual oil and asphaltic material are valuable components of the product for such purposes. I regard the use of the carbon product in the manufacture of briquettes as particularly important. This phase of my invention is described and claimed in application Serial No. 89,060, filed of even date herewith.

A typical ultimate analysis of the precipitated carbon, prepared according to the present invention, is given below:

Per cent Carbon 85.15

Hydrogen $.98 Oxygeiiiiniegeii-aiisiiliiifdiy difference) 7.87

The oil treated for the production of this carbon was pressure tar (residuum from pressure distillation of hydrocarbon oil) and had a gravity of 17 A. P. i.

The percentage composition of the-carbon product will vary somewhat with the nature of the oil from which it is prepared, but the percentages are generally of the same order as those just given. The acid-precipitated product contains a lower percentage of carbon and of hydrogen than the material which slowly settles out from the oil on standing without acid treatment. The acid-precipi tated product settles out rapidly from heavy oil in which it has been suspended by shaking or the like. In this respect, among others, it is different from lamp black, asphalt, and allied substances.

After extraction with carbon disulfid, the product remaining undissolved had the following composition:

Percent Carbon y 83.44 Hydrogen 4.89 Ash 2.84

Oxygen, nitrogen and sulfur (by difference) 8.83

ing) point. The fusing point may be between about 1G00 and 230 C., frequently approximating 175o C. The carbon productfree from oil may be between l5 and 30% soluble in carbon disulfid; the average solubility in this solvent is around 23%. The portion insoluble in carbon disulfid does not have a melting bint. This is determined by heating 'l gm. o if he product for 7 minutes in a covered Crucible heated by the full Bunsen iame. It appears that the carbon disulfid-soluble portion imparts fusibility to the mass and decomposes on heating, forming a residue having binding properties especially valuable in briquette making. The volatile matter in the carbon product before extraction with carbon disulfid may average around 12% by weight.

As indicated by the analyses above, there is not a marked difference in percentage composition between the extracted and the un- `i r extracted carbon. There is, however, considerable difference in their physical characteristics. The components removed by car-l bon disulfid appear to be of asphaltic nature, The residue is mostly non-asphaltic. lt may be said in general that the proportion of asphaltic and non-asphaltic matters in the precipitated carbon product is about 25: 75.

It will be understood that other equipment than that illustrated may be used in carry ing out my process. Various changes and alternative arrangements may be made in the procedure described, Within the scope of the appended claims, in which it is my intention to claim all novelty inherent in the invention as broadly as the prior art permits.

I claim:

l. As a new article of manufacture, carbo naceous material precipitated by a dilute acidic reagent from heavy residu of hydrocarbon oil cracking, characterized by a fusing point between about 160 and 230 C., and being about 15 to 30% soluble in carbon disulid.

2. As a new article of manufacture, carbonaceous material precipitated by a dilute acidic reagent from heavy residues of hydrocarbon oil cracking, characterized by a fusing point approsimating 175 C.. and' being about 23% soiuble in carbon disulfid.

3. As a new article of manufacture, carbonaceous material precipitated by a non-sludge forming acid from heavy residues of hydrocarbon oil cracking, and containing asphaltic components and non-asphaltic components, said asphaltic components being characterized by fusibility and the production of a binding substance'when subjected to heat.

4. As a new articie of manufacture carbonaceous material precipitated by addition of a small quantity of dilute sulphuric acid to the heavy residue of oil cracking containing about 25% of asphaltic components and 7 5%" of non-asphaltic components, said asphaltic components being characterized by fusibility and the production of a bindingsubstance when subjected to heat. i

5. As a new article of manufacture, carbonaceous material precipitated by commingling a small quantity of a dilute acidic material with a heavy residue from oil cracking, said material comprising about 25% by weight of asphaltic material and by weight of non-asphaltic material, said carbonaceous material being characterized by a fusing point between about 'and 230 C. and by being about 15% to 30% soluble in carbon disuiid.

6. As a new article of manufacture, carbonaceous inateriaiprecipitated by co gling a small quantity of a dilute acidic mate-` rial with a heavy residue from oil cracking, said material containin about 85% total carbon and characterizedgby "a fusing point ci about C., solubility to the extent of about 23% in carbon disuld, and by containin ,before extraction'with an organic solvent, a 12% by weight of volatile matter.

7 As a new article of manufacture, carbonaceo'us material precipitated by commingling a simail quantity of a dilute acidic material with a heavy residue from oil cracking,

ysaid material containing about 85% total carbon, and characterized by fusibility, by'only partial solubility in carbon disuld, and by a carbon content of aboutI 83% after extraction vith carbon disuld.

RLPHT. 0D. 

